CN111848963B - Preparation method of flame-retardant resin capable of being repeatedly processed and thermally cured at high temperature - Google Patents

Preparation method of flame-retardant resin capable of being repeatedly processed and thermally cured at high temperature Download PDF

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CN111848963B
CN111848963B CN202010677473.0A CN202010677473A CN111848963B CN 111848963 B CN111848963 B CN 111848963B CN 202010677473 A CN202010677473 A CN 202010677473A CN 111848963 B CN111848963 B CN 111848963B
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bmi
flame
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alcohol
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CN111848963A (en
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吴战鹏
张新芳
刘伟
张双琨
马翰林
赵京波
林红吉
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Hebei Kailuan Hangxiang New Materials Co ltd
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Shandong Hangxiang New Materials Co ltd
Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2385/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
    • C08J2385/02—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2485/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers
    • C08J2485/02—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers containing phosphorus

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

A preparation method of flame-retardant resin capable of being repeatedly processed and thermally set at high temperature belongs to the field of resin recycling and flame retardance. The method specifically comprises three parts: (1) and (3) performing side group functionalization on hexachlorocyclotriphosphazene HCCP to prepare a cyclophosphazene prepolymer CP-3AF containing three allyl groups and three conjugated double bond heterocycles. (2) The thermal reversibility is achieved by the Dield-Alder (DA) reaction of the conjugated double-bond heterocycle of CP-3AF with bismaleimide BMI, and the reverse reaction rDA. (3) At higher temperatures, the irreversible addition reaction of allyl groups to BMI will be triggered, creating a permanently crosslinked flame retardant network. The prepared repeatable processing thermal reversible crosslinking material has stable cycle performance and high carbon residue. The irreversible flame-retardant network after high temperature has high limit oxygen index (LOI is 28-39.8%), and the combustion grade is UL 94-V0.

Description

Preparation method of flame-retardant resin capable of being repeatedly processed and thermally cured at high temperature
Technical Field
The invention belongs to the field of resin recycling and flame retardance, and particularly relates to preparation of a cyclic phosphazene prepolymer (CP-3AF), preparation of a cyclic phosphazene based repeatedly-processable thermally reversible cross-linking material (r-CP-BMI) and preparation of a flame-retardant thermosetting resin material (i-CP-BMI). The finally obtained thermal reversible material has stable cycle performance, and the thermosetting material obtained after high-temperature treatment has excellent flame retardant property.
Background
Due to the rapid development of society, the consumption of materials is more and more, and the treatment of waste materials becomes a scientific problem. Especially, after the thermosetting resin is discarded, the thermosetting resin is more incinerated and buried, which not only wastes resources, but also causes serious pollution to the environment. Sustainable development of materials and recycling of resources are at a premium, and for this reason more and more reversible crosslinked materials are being researched and developed.
At present, the introduction of a reversible covalent bond into a high molecular material has become an effective method for preparing a reversible crosslinking material, wherein the Diels-Alder (DA) cycloaddition reaction has been widely applied to epoxy resin, polyurethane and bismaleimide resin. The DA-based cycloaddition reaction often causes inverse DA (rDA) reaction at a temperature higher than 100 ℃, so that the crosslinked polymer is depolymerized into an initial reactant again, and then the reversible crosslinked material can be constructed by DA reaction again at a low temperature.
However, the DA/rDA system-based thermoreversible material can cause depolymerization of the material and loss of a three-dimensional stable structure at a higher temperature, thereby causing flow and deformation, even causing fire, and bringing immeasurable consequences. Therefore, the problem can be effectively solved by designing a secondary reaction and introducing a flame-retardant substance on the thermo-reversible material of the DA/rDA system.
Allyl compounds are often used to modify bismaleimide resins, both of which tend to undergo addition reactions well above 150 ℃. Therefore, the conjugated diene heterocyclic compound and the allyl group are simultaneously introduced into the structure of the same compound, and the conjugated diene heterocyclic compound and the allyl group are crosslinked with the bismaleimide, so that the thermoreversible material can be converted into an irreversible crosslinking network, and the material can be ensured to maintain a three-dimensional stable structure through irreversible reaction when exposed to high temperature. Phosphazene substances are widely applied to flame retardant materials due to excellent flame retardant performance and flexible structure adjustability, wherein cyclic phosphazenes are more easily adjusted in the aspect of side group functionalization compared with polyphosphazenes, so that the cyclic phosphazenes are widely applied. Therefore, allyl and conjugated double bond heterocycle are simultaneously introduced to the cyclophosphazene and compounded with the bismaleimide, so that the integration of the thermoreversibility and the high-temperature irreversible flame retardant network can be realized, and the functionalized DA-based thermoreversible material is obtained.
Disclosure of Invention
The invention aims to provide a cyclic phosphazene thermally-reversible cross-linking material and a preparation method for converting the cyclic phosphazene thermally-reversible cross-linking material into an irreversible flame-retardant network at high temperature, so as to solve the problems of flowing and deformation of a DA-based thermally-reversible material caused by rDA reaction at high temperature and fire at higher temperature. According to the invention, allyl and conjugated double bond heterocycle are introduced on the cyclophosphazene through side group functionalization, and the cyclophosphazene and the bismaleimide are compounded to obtain the repeatedly processable thermally reversible crosslinking material, and a permanent crosslinking flame-retardant network can be generated through an olefin addition reaction when high temperature is encountered.
A preparation method of a flame-retardant resin which can be repeatedly processed and thermoset at high temperature is characterized by comprising the following specific steps:
(1) preparing a cyclic phosphazene prepolymer CP-3AF containing three allyl groups and three conjugated double bond heterocycles;
the structure of CP-3AF contains six pendant groups containing two different functional groups, three of which contain conjugated double-bonded heterocycles and the other three contain allylic functional groups.
The method comprises the following steps:
adding 1.05-2 molar equivalents of alcohol/phenol containing allyl into 1 molar equivalent of Na/NaH organic solvent to obtain sodium salt solution; wherein the allyl alcohol/phenol can be the same compound or a mixture of a plurality of compounds;
reacting the 6.5-12 molar equivalent of the sodium salt solution with 1 molar equivalent of Hexachlorocyclotriphosphazene (HCCP) at 40-70 ℃ for 10-120 hours; washing for several times by using deionized water and ethanol to obtain an intermediate product I;
adding 3 molar equivalents of thiol containing conjugated double bond heterocycle into 1 molar equivalent of the organic solution of the product I, reacting for 1-120 hours at 0-70 ℃ under ultraviolet light, and washing for 2-5 times by deionized water and ethanol to obtain CP-3 AF;
the second method comprises the following steps:
adding 3 mol equivalent of organic solution containing allyl alcohol/phenol sodium salt into 1 mol equivalent of HCCP, and reacting for 1-48 hours; with addition of 3.5-6 molar equivalents of conjugated double bond heterocycle-containing alcohol/amineSodium salt or adding 3.5-6 mol equivalent of alcohol/amine containing conjugated double bond heterocycle and K2CO3/Na2CO3Reacting the formed complex salt for 10-120 hours at 40-70 ℃, and washing for 2-5 times by deionized water and ethanol to obtain CP-3 AF.
The allyl-containing alcohol/phenol is one or a combination of the following: allyloxyethanol, allyl alcohol, eugenol, p-allylphenol, o-allylphenol.
The thiol containing heterocyclic ring with conjugated double bond is one or the combination of the following substances: furfuryl mercaptan, thiophenethiol, 2-thiophenemethyl mercaptan.
The alcohol/amine containing conjugated double bond heterocycle is one or a combination of the following substances: furfuryl alcohol, 2- (1-pyrrolyl) -ethanol, 2- (hydroxymethyl) thiophene, furfuryl amine, thienylmethylamine, 5-methylfurfuryl amine, 2-thienylmethylamine, 5-ethylfurfuryl amine, 1-aminopyrrole, 2- (1-pyrrolyl) -ethylamine.
The organic solution is prepared by adopting one of the following solvents: tetrahydrofuran, dichloromethane, trichloromethane, acetone, 1-4-dioxane, chlorobenzene, dichlorobenzene, dimethylformamide and dimethyl sulfoxide.
(2) Preparation of cyclic phosphazene-based thermally reversible material r-CP-BMI:
mixing the prepared CP-3AF and Bismaleimide (BMI) according to the molar ratio of allyl to maleimide functional group of 1:1, melting and stirring uniformly at the temperature of 100-145 ℃, then cooling to below 85 ℃, and keeping for 3-60 hours to obtain the cyclic phosphazene-based thermoreversible material;
each cycle was prepared by heating r-CP-BMI to 100 ℃ and 145 ℃ to depolymerize for 1-30 minutes and then cure at 85 ℃ for 120 hours.
The Bismaleimide (BMI) is one or a combination of several of the following substances: 4,4' -bismaleimidodiphenylmethane, N, N ' -1, 3-phenylenebismaleimide, 1, 4-bis (maleimido) butane, N, N ' -1, 4-phenylenedimaleimide, 1, 6-bismaleimidohexane.
The preparation method for converting r-CP-BMI into the irreversible cross-linked flame-retardant material (i-CP-BMI) comprises the following steps:
heating the r-CP-BMI to the temperature of over 150 ℃ to obtain a permanent cross-linking material i-CP-BMI; the preferred temperature is 150 ℃ to 190 ℃ and the preferred time is between 1 minute and 60 hours.
The material obtained by the invention can be used as a repeatedly-processable thermally reversible cross-linked material, and can generate a permanent cross-linked flame-retardant network through an olefin addition reaction when the material encounters a high temperature of more than 150 ℃ to be used as a flame retardant.
The cyclic phosphazene thermoreversible material prepared by the invention still has almost the same performance as the original material after repeated processing. After high-temperature treatment, a permanently crosslinked flame-retardant network is obtained through irreversible addition reaction, so that the defects of high-temperature flow and deformation of the DA system thermoreversible material are effectively overcome, and the flame-retardant property of the material is greatly improved due to the introduction of the phosphazene.
Detailed Description
The present invention will be further described with reference to some examples, but the present invention is not limited to only the following examples.
Example 1
1.5 molar equivalents of p-allylphenol were gradually added to 1 molar equivalent of metallic sodium containing tetrahydrofuran and reacted for 48 hours until all of the metallic sodium was consumed.
9 molar equivalents of the above sodium salt solution was added to 1 molar equivalent of hexachlorocyclotriphosphazene and reacted at 50 ℃ for 120 hours. The resulting product solution was washed four times with deionized water and ethanol to give product i.
Adding 3 molar equivalents of thiophenethiol into 1 molar equivalent of dimethyl sulfoxide solution of the product I, and reacting for 72 hours at 40 ℃ under ultraviolet light to obtain CP-3 AF.
CP-3AF and 4,4' -bismaleimidodiphenylmethane were reacted with maleimide functional group 1:1 at 130 ℃ for 20 minutes, followed by curing at 60 ℃ for 30 hours, to give a thermoreversibly crosslinked polymer r-CP-BMI. Each cycle was prepared by grinding the sample after the mechanical property test was performed the last time, depolymerizing at 130 ℃ for 15 minutes, and curing again at 60 ℃ for 30 hours.
The mechanical property of the prepared r-CP-BMI can reach 30MPa, the mechanical property can still reach 28MPa after secondary circulation, and the mechanical property can still reach 27MPa after five times of circulation. The carbon residue is up to 55% at 800 ℃.
And heating the r-CP-BMI at 160 ℃ for 10 hours to obtain the irreversible cross-linked flame-retardant material i-CP-BMI.
The prepared i-CP-BMI Limiting Oxygen Index (LOI) reaches 29 percent, the UL-94 level reaches V-0, and the flame retardant property is excellent.
Example 2
0.75 molar equivalent of eugenol and 0.75 molar equivalent of allyloxyethanol are mixed uniformly, and then added gradually to 1 molar equivalent of sodium hydride containing tetrahydrofuran, and reacted for 48 hours until all the sodium hydride is consumed.
9 molar equivalents of the above sodium salt solution was added to 1 molar equivalent of hexachlorocyclotriphosphazene and reacted at 60 ℃ for 90 hours. The resulting product solution was washed four times with deionized water and ethanol to give product i.
Adding 1.5 molar equivalents of thiophenethiol and 1.5 molar equivalents of furfuryl mercaptan into 1 molar equivalent of the tetrahydrofuran solution of the product I, and reacting at 40 ℃ for 72 hours under ultraviolet light to obtain CP-3 AF.
CP-3AF and 1, 4-bis (maleimido) butane were hybridized with maleimide functional group 1:1 at 145 ℃ for 15 minutes, followed by curing at 70 ℃ for 20 hours, to give a thermoreversibly crosslinked polymer r-CP-BMI. Each cycle was prepared by grinding the sample after the mechanical property test was performed the last time, depolymerizing at 130 ℃ for 15 minutes, and curing again at 70 ℃ for 20 hours.
The mechanical property of the prepared r-CP-BMI can reach 35MPa, the r-CP-BMI still reaches 34MPa after secondary circulation, and the r-CP-BMI still reaches 31MPa after five times of circulation. The carbon residue is up to 52% at 800 ℃.
And heating the r-CP-BMI at 150 ℃ for 20 hours to obtain the irreversible cross-linked flame-retardant material i-CP-BMI.
The prepared i-CP-BMI Limited Oxygen Index (LOI) is as high as 28.3 percent, the UL-94 grade reaches V-0, and the flame retardant property is excellent.
Example 3
After 0.75 molar equivalent of eugenol and 0.75 molar equivalent of o-allylphenol are uniformly mixed, the mixture is gradually added into 1 molar equivalent of tetrahydrofuran-containing sodium metal and reacts for 48 hours until all the sodium metal is consumed, and then the mixed sodium salt of the eugenol and the o-allylphenol is obtained.
The 3 molar equivalents of the mixed sodium salt were added to 1 molar equivalent of hexachlorocyclotriphosphazene and reacted for 24 hours.
Mixing 6 molar equivalents of furfuryl alcohol and 6 molar equivalents of K2CO3After being mixed evenly, the mixture is added into the cyclophosphazene substituted by the mixed sodium salt and reacts for 120 hours at 65 ℃ to obtain CP-3 AF.
CP-3AF and N, N' -1, 4-phenylenedimaleimide are reacted with maleimide functional groups 1:1 at 130 ℃ for 15 minutes, followed by curing at 70 ℃ for 20 hours, to give a thermoreversibly crosslinked polymer r-CP-BMI. Each cycle was prepared by grinding the sample after the mechanical property test was performed the last time, depolymerizing at 130 ℃ for 15 minutes, and curing again at 70 ℃ for 20 hours.
The mechanical property of the prepared r-CP-BMI can reach 28MPa, the r-CP-BMI still reaches 26MPa after secondary circulation, and the r-CP-BMI still reaches 25MPa after five times of circulation. The carbon residue is up to 57% at 800 ℃.
And heating the r-CP-BMI at 160 ℃ for 20 hours to obtain the irreversible cross-linked flame-retardant material i-CP-BMI.
The prepared i-CP-BMI Limited Oxygen Index (LOI) is as high as 32.3 percent, the UL-94 grade reaches V-0, and the flame retardant property is excellent.
Example 4
1.5 molar equivalents of eugenol are gradually added into 1 molar equivalent of tetrahydrofuran-containing metal sodium, and the reaction is carried out for 48 hours until all the metal sodium is consumed, so as to obtain the eugenol sodium salt. The 2- (hydroxymethyl) thiophene sodium salt is prepared by the same method.
The 3 molar equivalents of eugenol sodium salt mentioned above were added to 1 molar equivalent of hexachlorocyclotriphosphazene and reacted for 24 hours. Then 6 molar equivalent of 2- (hydroxymethyl) thiophene sodium salt is added into the mixture to react for 120 hours at 60 ℃ to obtain CP-3 AF.
Mixing CP-3AF, 1, 6-bismaleimide n-hexane and 4,4' -bismaleimide diphenylmethane according to the ratio of conjugated double bond heterocycle and maleimide functional group 3: 2: 1 at 145 ℃ for 15 minutes, followed by curing at 75 ℃ for 30 hours to give a thermoreversibly crosslinked polymer r-CP-BMI. Each cycle was prepared by grinding the sample after the mechanical property test was performed the last time, depolymerizing at 130 ℃ for 15 minutes, and curing again at 75 ℃ for 30 hours.
The mechanical property of the prepared r-CP-BMI can reach 40MPa, the r-CP-BMI still reaches 39MPa after secondary circulation, and the r-CP-BMI still reaches 39MPa after five times of circulation. The carbon residue content is up to 59 percent at 800 ℃.
And heating the r-CP-BMI at 170 ℃ for 10 hours to obtain the irreversible cross-linked flame-retardant material i-CP-BMI.
The prepared i-CP-BMI Limited Oxygen Index (LOI) is up to 31.8 percent, the UL-94 grade reaches V-0, and the flame retardant property is excellent.
Example 5
1.5 molar equivalents of eugenol are gradually added into 1 molar equivalent of sodium hydride containing tetrahydrofuran and reacted for 48 hours until all the sodium hydride is consumed, thus obtaining the sodium eugenol salt.
Adding 6 molar equivalents of the sodium salt into 1 molar equivalent of hexachlorocyclotriphosphazene, and reacting at 65 ℃ for 100 hours to obtain a product I.
Uniformly mixing 1.5 molar equivalent furfuryl mercaptan and 1.5 molar equivalent thiophenethiol, adding the mixture into the product I, and reacting at 30 ℃ for 120 hours to obtain CP-3 AF.
Mixing CP-3AF, 4,4 '-bismaleimide diphenylmethane and N, N' -1, 4-phenylene bismaleimide according to a conjugated double-bond heterocycle and a maleimide functional group 2: 1:1 at 145 ℃ for 15 minutes, followed by curing at 70 ℃ for 20 hours, to give a thermoreversibly crosslinked polymer r-CP-BMI. Each cycle was prepared by grinding the sample after the mechanical property test was performed the last time, depolymerizing at 130 ℃ for 15 minutes, and curing again at 70 ℃ for 20 hours.
The mechanical property of the prepared r-CP-BMI can reach 44MPa, the r-CP-BMI still reaches 43MPa after secondary circulation, and the r-CP-BMI still reaches 42MPa after five times of circulation. The carbon residue is up to 60% at 800 ℃.
And heating the r-CP-BMI at 170 ℃ for 20 hours to obtain the irreversible cross-linked flame-retardant material i-CP-BMI.
The prepared i-CP-BMI Limited Oxygen Index (LOI) is up to 35.4 percent, the UL-94 grade reaches V-0, and the flame retardant property is excellent.
The prepared repeatable processing thermal reversible crosslinking material has stable cycle performance and high carbon residue. The irreversible flame-retardant network after high temperature has high limit oxygen index (LOI is 28-39.8%), and the combustion grade can be UL 94-V0. The conversion from the thermal reversible material to the permanent crosslinking material effectively avoids the defects of flowing and deformation of the DA/rDA-based thermal reversible material at high temperature, and the introduction of the phosphazene also avoids the risk of fire caused by high temperature.

Claims (5)

1. A preparation method of a flame-retardant resin which can be repeatedly processed and thermoset at high temperature is characterized by comprising the following specific steps:
(1) preparing a cyclic phosphazene prepolymer CP-3AF containing three allyl groups and three conjugated double bond heterocycles;
(2) preparation of cyclic phosphazene-based thermally reversible material r-CP-BMI:
mixing the prepared CP-3AF and bismaleimide BMI according to the molar ratio of allyl to maleimide functional group of 1:1, melting and stirring uniformly at the temperature of 100-145 ℃, then cooling to below 85 ℃, and keeping for 3-60 hours to obtain the cyclic phosphazene-based thermoreversible material;
(3) heating the r-CP-BMI to the temperature of over 150 ℃ to obtain a permanent cross-linking material i-CP-BMI;
heating r-CP-BMI to the temperature of 150-190 ℃ for 1 min to 60 h to obtain a permanent cross-linking material i-CP-BMI;
the preparation method of the cyclic phosphazene prepolymer CP-3AF containing three allyl groups and three conjugated double bond heterocycles in the step (1) comprises the following steps:
the method comprises the following steps:
adding 1.05-2 molar equivalents of alcohol/phenol containing allyl into 1 molar equivalent of Na/NaH organic solvent to obtain sodium salt solution; wherein the allyl alcohol/phenol can be the same compound or a mixture of a plurality of compounds;
reacting the sodium salt solution with 6.5-12 molar equivalents with hexachlorocyclotriphosphazene HCCP with 1 molar equivalent at 40-70 ℃ for 10-120 hours; washing for several times by using deionized water and ethanol to obtain an intermediate product I;
adding 3 molar equivalents of thiol containing conjugated double bond heterocycle into 1 molar equivalent of the organic solution of the product I, reacting for 1-120 hours at 0-70 ℃ under ultraviolet light, and washing for 2-5 times by deionized water and ethanol to obtain CP-3 AF;
the second method comprises the following steps:
adding 3 molar equivalents of organic solution containing allyl alcohol/sodium phenolate to 1 molar equivalent of HCCP, and reacting for 1-48 hours; adding 3.5-6 mol equivalent of the sodium salt of the alcohol/amine containing the conjugated double bond heterocycle or adding 3.5-6 mol equivalent of the alcohol/amine containing the conjugated double bond heterocycle and K2CO3/Na2CO3Reacting the formed complex salt for 10-120 hours at 40-70 ℃, and washing for 2-5 times by deionized water and ethanol to obtain CP-3 AF.
2. The method of claim 1, wherein the allyl-containing alcohol/phenol is one or a combination of the following: allyloxyethanol, allyl alcohol, eugenol, p-allylphenol, o-allylphenol;
the thiol containing heterocyclic ring with conjugated double bond is one or the combination of the following substances: furfuryl mercaptan, thiophenethiol, 2-thiophenemethyl mercaptan;
the alcohol/amine containing conjugated double bond heterocycle is one or a combination of the following substances: furfuryl alcohol, 2- (1-pyrrolyl) -ethanol, 2- (hydroxymethyl) thiophene, furfuryl amine, thienylmethylamine, 5-methylfurfuryl amine, 5-ethylfurfuryl amine, 1-aminopyrrole, 2- (1-pyrrolyl) -ethylamine;
the organic solution is prepared by adopting one of the following solvents: tetrahydrofuran, dichloromethane, trichloromethane, acetone, 1-4-dioxane, chlorobenzene, dichlorobenzene, dimethylformamide and dimethyl sulfoxide.
3. The method of claim 1, wherein the Bismaleimide (BMI) is one or a combination of the following materials: 4,4' -bismaleimidodiphenylmethane, N, N ' -1, 3-phenylenebismaleimide, 1, 4-bis (maleimido) butane, N, N ' -1, 4-phenylenedimaleimide, 1, 6-bismaleimidohexane.
4. An irreversible crosslinked flame retardant material i-CP-BMI prepared according to the method of any one of claims 1 to 3.
5. Use of a flame retardant resin capable of being processed repeatedly and thermoset at high temperature, prepared by the process according to any one of claims 1 to 3, as a thermally reversible cross-linked material capable of being processed repeatedly, when subjected to high temperatures of greater than 150 ℃, to form a permanently cross-linked flame retardant network by addition of an olefin, as a flame retardant.
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